Process for the preparation of metal complexes of isoindolinazines

ABSTRACT

Process for the preparation of 1:1 metal complexes of azines of the formula ##STR1## in which R 1  is an H atom or an alkyl or aryl group, R 2  is an isocyclic or heterocyclic radical with a hydroxyl or mercapto group adjacent to the azomethine group, Y&#39; is the radical of a methylene-active compound or of an aryl-or heteroaryl-amine and the ring A can have substituents which do not confer solubility in water, which comprises heating a hydrazone of the formula ##STR2## with an isoindolinone of the formula ##STR3## in which R 1 , R 2 , A and Y&#39; are as defined, in the presence of a metal donor, in a polar organic solvent.

This is a divisional of application Ser. No. 242,006, filed on Mar. 9,1981, now abandoned.

British Patent Specification No. 1,467,595 describes the preparation of1:1 metal complexes of azines of the formula ##STR4## in which R₁ is anH atom or an alkyl or aryl group, R₂ is an isocyclic or heterocyclicradical with a hydroxyl group adjacent to the azomethine group, Y is theradical of a methylene-active compound or of an aryl- orheteroaryl-amine and the ring A can have substituents which do notconfer solubility in water, by condensing a hydrazone of the formula##STR5## with an isoindoline of the formula ##STR6## and treating thecompounds of the formula (1) with metal donors. Although this gives thecompound of the formula (1) in good yield, the 1:1 nickel complexesobtained therefrom give colourations of unsatisfactory purity andinadequate fastness properties in plastics and surface coatings. Thecondensation of the isoindoline of the formula (3) with the hydrazone ofthe formula (2), in the presence of metal salts, likewise leads tounsatisfactory results.

It has now been found that the 1:1 metal complexes of the azines of theformula ##STR7## in which A and R₁ are as defined, Q is an isocyclic orheterocyclic radical with a hydroxyl or mercapto group adjacent to theazomethine group and Y' is the radical of a methylene-active compound orof an aryl- or heteroaryl-amine, are obtained in especially high purityby heating a hydrazone of the formula ##STR8## with an isoindolinone ofthe formula ##STR9## in the presence of a metal donor, in a polarorganic solvent.

The novel 1:1 metal complexes of azines of the formula ##STR10## inwhich A, R₁ and Y' are as defined above and B is an isocyclic orheterocyclic radical, which complexes are obtainable by the processaccording to the invention, are a further subject of the invention. R₁is, for example, an H atom or preferably a methyl group. B is a phenylor naphthalene radical or a 5- or 6-membered heterocyclic ring which hasan O, S or especially N atom in the α- or γ-position to the C atom onwhich the mercapto group is located, and which, if desired, alsocontains a further N atom in the ring and, if desired, contains a fusedbenzene ring and/or a further heterocyclic ring.

B is preferably a heterocyclic radical, for example of the pyrimidine,quinoline or preferably pyrazole series, and in particular aheterocyclic radical of the formula ##STR11## in which R₄ is an alkylgroup having 1-4 C atoms, an alkoxycarbonyl group having 2-6 C or acarbamoyl group, X₁ is an H, chlorine or bromine atom, a nitro,trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy oralkylsulfamoyl group having 1-4 C, an alkanoylamino, alkylcarbamoyl oralkoxycarbonyl group having 2-6 C, or a phenoxy, benzoylamino,phenylcarbamoyl, phenylsulfamoyl or phenylazo group which isunsubstituted or substituted by chlorine or bromine atoms or methylgroups, and X₂ is an H, chlorine or bromine atom or an alkyl or alkoxygroup having 1-4 C. The formulae (1) and (7) in each case represent oneof the possible isomeric forms.

The hydrazones of the formula (5) are obtained by the known process ofreacting an oxo compound of the formula ##STR12## in which R₁ and Q areas defined, or its aldimine with hydrazine hydrate. Of particular valueare aldehydes or ketones of the formula ##STR13## in which R₃ is an Hatom or preferably a methyl group and B is a phenyl or naphthaleneradical or a 5- or 6-membered heterocyclic ring which has an O, S orespecially N atom in the α- or γ-position to the C atom on which thehydroxyl group is located, and, if desired, also contains a further Natom in the ring and, if desired, contains a fused benzene ring and/or afurther heterocyclic ring.

B is preferably a radical of the pyrazole, pyridine, pyrimidine,quinoline or coumarin series.

Oxo compounds of the formula ##STR14## are preferred.

Examples of oxo compounds are the aldehydes and ketones listed inBritish Pat. No. 1,467,595 and also1-phenyl-3-methyl-4-formyl-5-mercapto-pyrazole, 1-o-, m- orp-chlorophenyl-3-methyl-4-formyl-5-mercapto-pyrazole, 1-o-, m- orp-methylphenyl-3-methyl-4-formyl-5-mercapto-pyrazole,1-phenyl-3-methyl-4-acetyl-5-mercapto-pyrazole, 1-o-, m- orp-chlorophenyl-3-methyl-4-acetyl-5-mercapto-pyrazole, 1-o-, m- orp-methylphenyl-3-methyl-4-acetyl-5-mercapto-pyrazole,2-formyl-5,5-dimethyl-cyclohexyl-1,3-dione, 2-mercapto-benzaldehyde,2-mercapto-acetophenone, 3-acetyl-2,4-dimercapto-quinoline,3-formyl-2,4-dimercaptoquinoline, 3-formyl-2-mercapto-quinoline,3-formyl-2,4,6-trimercapto-pyrimidine,3-acetyl-2,4,6-trimercapto-pyrimidine, 4-mercaptocoumarin and2-formyl-1,3-dithiono-5,5-dimethylcyclohexane.

The isoindolinones of the formula (6) are obtained by the known processof condensing an isoindolinone of the formula ##STR15## aphthalodinitrile or an o-cyanobenzoic acid ester with a methylene-activecompound or an aryl- or heteroarylamine. Methylene-active compounds are,in particular, those of the formula

    NC--CH.sub.2 R'

in which R' is a cyano group, an alkoxycarbonyl, alkylcarbamoyl oralkanoyl group having 2-6 C, a benzoyl, carbamoyl or sulfamoyl group, abenzylcarbamoyl group or a phenylsulfamoyl or phenylsulfonyl group whichis unsubstituted or substituted by halogen atoms or alkyl groups having1-4 C, but especially a group of the formula ##STR16## in which X₁ andX₂ are defined and V is 0, S or NH.

Examples are the acetonitriles listed on page 7 of British PatentSpecification No. 1,467,595 and also cyanoacetic acido-chlorophenylamide, p-chlorophenylamide, m-chlorophenylamide,m-methylphenylamide, p-methylphenylamide, 3,4-dichlorophenylamide,3,5-dimethylphenylamide, 3,4-dimethylphenylamide,3-chloro-4-methylphenylamide, o-methoxyphenylamide,2,4-dimethoxyphenylamide, 2,5-dimethoxyphenylamide,p-acetylamino-phenylamide, p-benzoylaminophenylamide,3-chloro-4-p-chlorobenzoylaminophenylamide, 4-carbamoylphenylamide,4-sulfamoylphenylamide, 4-phenylazophenylamide, 4-phenoxyphenylamide,p-nitrophenylamide, 3-trifluoromethylphenylamide or2-chloro-5-trifluoromethyl-phenylamide, and 2-cyanomethyl-4-phenyl-,-4-p-nitrophenyl, -4-fluorophenyl- or -4-methylphenylthiazole.

Further possible methylene-active compounds are heterocyclic compoundscontaining one active methylene group in the heterocyclic ring, forexample those mentioned on pages 7 and 8 of British Patent SpecificationNo. 1,467,595, for example 2,4-dihydroxyquinoline,1-p-chlorophenyl-3-methyl-5-pyrazolone,1-p-methylphenyl-3-methyl-5-pyrazolone,1-phenyl-3-dichlorovinyl-5-pyrazolone and1-p-methylphenyl-3-dichlorovinyl-5-pyrazolone.

Examples of amines which donate the radical Y' are aromatic, butespecially heterocyclic, amines, preferably those in which the aminogroup is located directly on a 5-6-membered heterocyclic ring which cancontain 1-3 N atoms and also O and S atoms. A substituted orunsubstituted benzene nucleus can be fused to the heterocyclic parentnucleus. Examples are the amines listed on pages 6-7 of British PatentSpecification No. 1,467,595, and also 2-aminopyridine,2-amino-5-chloropyridine, diaminophthalazine,2-amino-4-hydroxyquinoline, 2,6-diaminopyridine and2-amino-4,5-dimethylthiazole.

The isoindolinones of the formula (12) are known. They are more readilyaccessible than corresponding diiminoisoindolines, and this represents afurther advantage of the novel process of preparation.

The metal donors used are preferably salts of zinc, cadmium, manganese,cobalt and iron, but especially of copper and nickel, or of mixtures ofthese metals. The formates, acetates or stearates of these metals areadvantageously used.

The reactions take place in a polar solvent, in particular one of ahydrophilic nature, for example an amide, such as dimethylformamide,formamide, dimethylacetamide or N-methylpyrrolidone, or also dimethylsulfoxide, acetonitrile or an alcohol, for example ethylcellosolve. Itis also possible to use a mixture of polar solvents.

The reaction temperature is advantageously between 100° and 200° C.

The metal complex obtained is isolated in the customary manner byfiltration. The material on the filter is washed thoroughly withsolvent. The pigment is obtained in excellent yield and purity and canbe used without further purification, in finely divided form, forcolouring high-molecular organic material, for example cellulose ethersand esters, such as ethylcellulose, acetylcellulose and nitrocellulose,polyamides, polyurethanes or polyesters, and natural resins or syntheticresins, for example aminoplasts, in particular urea/formaldehyde andmelamine/formaldehyde resins, alkyd resins, phenoplasts, polycarbonates,polyolefins, such as polystyrene, polyvinyl chloride, polyethylene,polypropylene, polyacrylonitrile and polyacrylic acid esters,thermoplastic or curable acrylic resins, rubber, casein, silicone andsilicone resins, individually or in mixtures. The high-molecularcompounds mentioned can be in the form of plastic masses or melts or inthe form of spinning solutions, surface coatings or printing inks.Depending on the intended use, it proves advantageous to use thepigments as toners or in the form of preparations.

The pigment can be employed in the form in which it is obtained in thesynthesis, or in a lightly ground form, in which case it produces opaquefinal colourations. However, it can also be subjected to intensivegrinding, in which case transparent final colourations, for exampleintensely coloured metallic-effect coatings, are obtained.

Pastes of the pigments in surface coatings are distinguished byfavourable flow properties.

The colourations obtained, for example in plastics, fibres and surfacecoatings, are distinguished by high colour intensity, high purity ofcolour shade, good dispersibility and good fastness to overcoating,migration, heat, light and weather, and also by a good gloss.

In addition to the purity of the end product obtained, furtheradvantages of the process according to the invention are that productssubstituted in the benzene ring A, and those in which Y' is the radicalof a particularly active methylene group, can also be prepared easily.

The success of the process according to the invention is surprisingbecause, hitherto, only reactions of the carbonyl group of isoindolineswere known, in which the keto group is first converted to a reactivederivative, for example an imide-chloride or iminoether. Therefore, itcould not be expected that isoindolinones of the formula (4) would becapable of reacting directly in a template reaction with hydrazones.

In the following examples, percentages are by weight and degrees aredegrees centigrade.

EXAMPLE 1

6.5 g (0.03 mol) of 2,4-dihydroxyquinoline-3-acetylhydrazone and 7.8 gof nickel acetate.4 H₂ O (0.315 mol) are dissolved in 150 ml ofN-methylpyrrolidone and the solution is warmed to 60° C. 9.7 g of1-cyano-N-p-chlorophenylcarbamoylmethylene)-isoindolin-3-one are thenadded. The suspension is warmed to 150° C. and stirred for 1 hour at150°-155° C. It is filtered hot (80° C.) and the residue is washed withN-methylpyrrolidone and ethanol. After drying at 80° C. in vacuo, 11.34g (65.3% of theory) of a red metal complex of the composition C₂₈ H₁₇ClN₆ O₃ Ni and of the formula ##STR17## are obtained.

Microanalysis: C₂₈ H₁₇ ClN₆ O₃ Ni (MW 579.65): % calculated C 58.02; H2.96; N 14.50; Cl 6.12; Ni 10.13; % found C 58.1 H 3.2 N 14.7 Cl 5.7 Ni9.95

EXAMPLE 2

1.32 g (0.007 mol) of dichlorosalicylaldehyde-hydrazone and 1.83 g(0.00735 mol) of nickel acetate. 4H₂ O are suspended in 60 ml ofN-methylpyrrolidone and the suspension is warmed to 60° C. 2.00 g (0.007mol) of 1-(cyano-2-benzimidazolyl-methylene)-3-isoindolinone are addedand the mixture is heated to 150° C. After stirring for 2 hours at150°-155° C., the reaction mixture is cooled to 35° C. and filtered. Theresidue is washed successively with N-methylpyrrolidone and ethanol anddried overnight in vacuo at 80° C. 1.4 g (36.5% of theory) of the nickelcomplex of the formula ##STR18## are obtained.

Microanalysis: C₂₄ H₁₁ N₆ OCl₂ Ni: calculated C 54.49%; H 2.10%; N15.89%; Cl 13.4% Ni; 11.10%; found C 54.6%; H 2.3%; N 16.1%; Cl 13.6%Ni; 11.4%

The above metal complex colours plastics and surface coatings in red,covering shades with excellent fastness properties.

EXAMPLE 3

1.3 g (0.006 mol) of 2,4-dihydroxy-3-acetylquinoline-hydrazone and 1.57g (0.0063 mol) of nickel acetate. 4H₂ O are heated to 60° C. in 50 ml ofN-methylpyrrolidone, with stirring. 1.92 g (0.006 mol) of1-(5'-acetylamino-2'-benzoxazolyl-imino)-3-isoindolinone, prepared from1-imino-3-oxo-isoindoline and 5-acetylamino-2-amino-benzoxazole, arethen added and the mixture is warmed to 140° C. After the reactionmixture has been left to react for 2.5 hours at 140°-45° C., it iscooled to 80° C. and filtered and the reaction product is washedN-methylpyrrolidone and spirit. After drying at 80° C. in vacuo, 3.06 g(88.5% of theory) of an orange metal complex of the composition C₂₈ H₁₉N₇ O₄ Ni and of the formula ##STR19## are obtained.

Microanalysis: C₂₈ H₁₉ N₇ O₄ Ni MW 576: calculated C 58.36%; H 3.32%; N17.02%; Ni 10.19%; found C 58.2%; H 3.5%; N 17.2%; Ni 10.0%

The above pigment colours plastics and surface coatings in yellowishorange shades with excellent fastness properties.

EXAMPLE 4

1.75 g (0.008 mol) of 4-hydroxy-3-acetylcoumarin-hydrazone and 2.1 g(0.0084 mol) of nickel acetate are suspended in 60 ml ofN-methylpyrrolidone and the suspension is then warmed to 60° C. Theresulting suspension is treated with 2.32 g (0.008 mol) of1-(2',4'-dioxo-quinolin-3'-ylidene)-3-isoindolinone, prepared from1-imino-3-oxoisoindoline and 2,4-dihydroxyquinoline, and heated to 140°.The mixture is left to react for 2 hours at 140°-45° C. and the metalcomplex which has precipitated out is then filtered off from the motherliquor. After washing with N-methylpyrrolidone and spirit and drying invacuo at 80° C., 3.0 g (68.5% of theory) of a red metal complex pigmentof the formula ##STR20## are obtained. The above metal complex coloursplastics and surface coatings in pure red shades with excellent fastnessproperties.

Microanalysis: C₂₇ H₁₄ N₄ O₅ Ni: MW 533 calculated C 60.83%; H 2.65%; N10.51%; Ni 11.01%; found C 60.9%; H 2.4%; N 10.8%; Ni 10.9%

EXAMPLE 5

1.68 g (0.006 mol) of 2,4-dihydroxy-3-benzoylquinoline-hydrazone and1.57 g (0.0063 mol) of nickel acetate 4H₂ O are suspended in 50 ml ofN-methylpyrrolidone and the suspension is warmed to 60° C. 1.95 g (0.006mol) of 1-(cyano-N-p-chlorophenylcarbamoyl-methylene)-isoindolin-3-oneare then added. The suspension is warmed to 145° C. and stirred for 11/2hours at 145°-150° C. It is filtered hot (80° C.) and the residue iswashed with N-methylpyrrolidone and ethanol. After drying at 80° C. invacuo, 2.34 g (61% of theory) of a red metal complex of the formula##STR21## are obtained.

Microanalysis: C₃₃ H₁₉ ClN₆ O3Ni (sic): MW 642 calculated C 61.77%; H2.98%; N 13.1%; CL 5.53%; Ni 9.15%; found C 61.2%; H 3.00%; N 13.1%; Cl5.4%; Ni 9.42%

The above metal complex pigment colours plastics and surface coatings inthe pure red shades with excellent fastness properties.

EXAMPLE 6

1.95 g (0.008 mol) of2-anilinomethylene-1,3-dioxo-5,5-dimethyl-cyclohexane, prepared fromaniline, orthoformic acid ester and 1,3-dioxo-5,5-dimethyl-cyclohexane,are dissolved in 50 ml of dimethylformamide. After 0.4 ml (0.008 mol) ofhydrazine hydrate has been added, the mixture is stirred at roomtemperature for 1 hour. 2.1 g (0.0084 mol) of nickel acetate. 4H₂ O arethen added and the mixture is warmed to 60° C. It is then treated with2.29 g (0.008 mol) of 1-(cyanobenzimidazolyl-methylene)-3-isoindolinoneand heated to 135° C. After 21/2 hours, the reaction mixture is cooledto 80° C. and the metal complex which has precipitated out is filteredoff. After washing with dimethylformamide and spirit and drying at 80°C. in vacuo, 3.5 g (86.3% of theory) of an orange compound of theformula ##STR22## are obtained.

Microanalysis: C₂₆ H₂₀ N₆ O₂ Ni: MW 507.2 calculated C 61.57%; H 3.97%;N 16.57%; Ni 11.58%; found C 61.4%; H 4.1%; N 16.8%; Ni 11.6%

The above complex colours plastics and surface coatings in the pureyellowish orange shades with excellent fastness properties.

EXAMPLE 7

1.95 g (0.008 mol) of2-anilinomethylene-1,3-dioxo-5,5-dimethyl-cyclohexane are dissolved in50 ml of N-methylpyrrolidone and treated with 0.4 ml (0.008 mol) ofhydrazine hydrate and the mixture is stirred at room temperature for 1hour. 2.1 g (0.0084 mol) of nickel acetate. 4H₂ O are added and themixture is warmed to 60° C. 3.2 g (0.008 mol) of1-benzimidazolylimino-4,5,6,7-tetrachloro-3-oxo-isoindoline are thenintroduced and the mixture is warmed to 145° C. It is stirred for 1 hourat the same temperature and then cooled (to 80° C.). The metal complexwhich has precipitated out is filtered off, washed withN-methylpyrrolidone and ethanol and dried overnight at 80° C. in vacuo.3.9 g (78.5% of theory) of a red pigment of the formula, ##STR23## areobtained, which colours plastics and surface coatings in red shades withexcellent fastness properties.

Microanalysis: C₂₄ H₁₆ Cl₄ N₆ O₂ Ni: MW 621 calculated C 46.42%; H2.60%; N 13.53%; Cl 22.84%; Ni 9.45%; found C 46.7%; H 2.7%; N 13.8%; Cl22.3%; Ni 9.36%

EXAMPLE 8

2.35 g (0.008 mol) of1-phenyl-3-methyl-4-anilinomethylene-5-mercaptopyrazole are dissolved in50 ml of dimethylformamide. After 0.4 ml (0.008 mol) of hydrazinehydrate has been added, the mixture is stirred at room temperature for 1hour and then treated with 2.1 g (0.0084 mol) of nickel acetate. 4H₂ Oand warmed to 60° C. 2.22 g (0.008 mol) of1-(cyano-benzimidazolylmethylene)-3-oxo-isoindoline are then introducedand the mixture is heated to 130° C. After a reaction time of 2 hours at130°-135° C., the mixture is cooled to 80° C. and filtered. Thefiltration residue is washed with dimethylformamide and ethanol anddried overnight at 80° C. in vacuo. 2.8 g (63% of theory) of a red metalcomplex of the formula ##STR24## are obtained.

Microanalysis: C₂₈ H₁₈ N₈ SNi: MW 557 calculated C 60.35%; H 3.26%; N20.11%; S 5.75%; Ni 10.54%; found C 60.3%; H 3.4%; N 20.0%; S 5.2%; Ni10.3%

EXAMPLE 9-76

Analogously to Examples 1-8, further 1:1 nickel complexes are obtainedby condensing the hydrazone of the oxo compounds indicated in column 2of Table 1 with the isoindolinone of the formula ##STR25## the latterhaving been obtained by condensing the 3-iminoisoinidolinone mentionedin column 3 with the compounds YH₂ listed in column 4. Column 5 givesthe shade in PVC.

                                      TABLE 1                                     __________________________________________________________________________    Ex-                                 Shade                                     ample                               in                                        No. Oxo compound                                                                           Isoindolinone                                                                        YH.sub.2        PVC                                       __________________________________________________________________________     9  1-p-Tolyl-3-                                                                           3-Imino-                                                                             Cyanoacet-      red                                           methyl-4-ace-                                                                          isoindolinone                                                                        anilide                                                       tyl-pyrazol-5-                                                                one                                                                       10  1-p-Chloro-                                                                            3-Imino-                                                                             Cyanoacetic     scarlet                                       phenyl-3-methyl                                                                        isoindolinone                                                                        acid p-                                                       4-formyl-pyra-  chloroanil-                                                   zol-5-one       ide                                                       11  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Ethyl cyano-    red                                           dihydroxy-                                                                             isoindolinone                                                                        acetate                                                       quinoline                                                                 12  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             isoindolinone                                                                        acid ethyl-                                                   quinoline       amide                                                     13  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Acetoaceto-     red                                           dihydroxy-                                                                             isoindolinone                                                                        nitrile                                                       quinoline                                                                 14  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             isoindolinone                                                                        acid p-                                                       quinoline       methoxy-                                                                      anilide                                                   15  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             isoindolinone                                                                        acid benzyl-                                                  quinoline       amide                                                     16  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Benzoyl-        red                                           dihydroxy-                                                                             isoindolinone                                                                        acetonitrile                                                  quinoline                                                                 17  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanomethane-   red                                           dihydroxy-                                                                             isoindolinone                                                                        p-tolyl-sul-                                                  quinoline       fonamide                                                  18  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanomethane-   red                                           dihydroxy-                                                                             isoindolinone                                                                        p-chloro-                                                     quinoline       phenyl-sul-                                                                   fonamide                                                  19  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             isoindolinone                                                                        acid p-sul-                                                   quinoline       famoylanil-                                                                   ide                                                       20  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             isoindolinone                                                                        acid p-car-                                                   quinoline       bamoylanil-                                                                   ide                                                       21  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Phenylsul-      red                                           dihydroxy-                                                                             isoindolinone                                                                        fonylaceto-                                                   quinoline       nitrile                                                   22  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-ben-                                                   quinoline       zoylamino-                                                                    anilide                                                   23  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-ace-                                                   quinoline       tylamino-                                                                     anilide                                                   24  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     orange                                        dihydroxy-                                                                             4,5,6,7-tetra-                                                                       acid p-chloro-                                                quinoline                                                                              chloro-iso-                                                                          anilide                                                                indolin-1-one                                                    25  3-Acetyl-2,4-                                                                          3-Imino- , -                                                                         Cyanoacetic     orange                                        dihydroxy-                                                                             dimethoxy- , -                                                                       acid p-chloro-                                                quinoline                                                                              dichloro-iso-                                                                        anilide                                                                indolinone                                                       26  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Cyano-        violet                                        dihydroxy-                                                                             4,5,6,7-tetra-                                                                       methyl-benzi-                                                 quinoline                                                                              chloro-iso-                                                                          midazole                                                               indolinone                                                       27  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid m-chloro-                                                quinoline       anilide                                                   28  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     scarlet                                       dihydroxy-                                                                             indolinone                                                                           acid 3',4'-                                                   quinoline       dichloro-                                                                     anilide                                                   29  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Cyano-        red                                           dihydroxy-                                                                             indolinone                                                                           methylbenzi-                                                  quinoline       midazole                                                  30  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Cyano-        red                                           dihydroxy-                                                                             indolinone                                                                           methyl-benzo-                                                 quinoline       thiazole                                                  31  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Cyano-        scarlet                                       dihydroxy-                                                                             indolinone                                                                           methyl-ben-                                                   quinoline       zoxazole                                                  32  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetan-    red                                           dihydroxy-                                                                             indolinone                                                                           ilide                                                         quinoline                                                                 33  1-p-Chlorophenyl-                                                                      3-Imino-iso-                                                                         Cyanoacetic     red                                           3-methyl-4-ace-                                                                        indolinone                                                                           acid p-acet-                                                  tyl-pyrazol-5-  ylaminoanil-                                                  one             ide                                                       34  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-nitro-                                                 quinoline       anilide                                                   35  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-phenyl-                                                quinoline       azoanilide                                                36  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     scarlet                                       dihydroxy-                                                                             indolinone                                                                           acid m-tri-                                                   quinoline       fluoromethyl-                                                                 anilide                                                   37  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-phen-                                                  quinoline       oxyanilide                                                38  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid 3'-                                                      quinoline       chloro-4'-                                                                    methylanil-                                                                   ide                                                       39  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid acetyl-                                                  quinoline       aminoanilide                                              40  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-phenyl-                                                quinoline       sulfamoyl-                                                                    anilide                                                   41  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid p-phenyl-                                                quinoline       carbamoyl-                                                                    anilide                                                   42  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Cyanoacetic     red                                           dihydroxy-                                                                             indolinone                                                                           acid o-eth-                                                   quinoline       oxycarbonyl-                                                                  anilide                                                   43  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Cyano-        red                                           dihydroxy-                                                                             indolinone                                                                           methyl-4-p-                                                   quinoline       fluoro-                                                                       phenyl-thia-                                                                  zole                                                      44  3-Acetyl-2,4-                                                                          3-Imino-5,6-                                                                         Barbituric      orange                                        dihydroxy-                                                                             dichloro-iso-                                                                        acid                                                          quinoline                                                                              indolinone                                                       45  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         1-p-Tolyl-3-    Bordeaux                                      dihydroxy-                                                                             indolinone                                                                           β,β-dichloro-                                                                       red                                           quinoline       vinyl-pyrazol-                                                                5-one                                                     46  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         Barbituric      red                                           dihydroxy-                                                                             indolinone                                                                           acid                                                          quinoline                                                                 47  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         1-Phenyl-3-     red                                           dihydroxy-                                                                             indolinone                                                                           methyl-pyra-                                                  quinoline       zol-5-one                                                 48  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Barbituric      orange                                        dihydroxy-                                                                             4,5,6,7-tetra-                                                                       acid                                                          quinoline                                                                              chloro-iso-                                                                   indolinone                                                       49  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Cyanomethyl-  violet                                        dihydroxy-                                                                             4,5,6,7-tetra-                                                                       benzimidazole                                                 quinoline                                                                              chloro-iso-                                                                   indolinone                                                       50  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             4,5,6,7-tetra-                                                                       acid 2',-5'-                                                  quinoline                                                                              chloro-iso-                                                                          dimethoxy-                                                             indolinone                                                                           anilide                                                   51  3-Acetyl-2,4-                                                                          3-Imino-                                                                             Cyanoacetic     red                                           dihydroxy-                                                                             4,5,6,7-tetra-                                                                       acid 3',4'-                                                   quinoline                                                                              chloro-iso-                                                                          dimethyl-                                                              indolinone                                                                           anilide                                                   52  2,4,6-Trihydroxy-                                                                      3-Imino-                                                                             2-Aminoimid-    orange                                        5-acetylpyrim-                                                                         4,5,6,7-tetra-                                                                       azole                                                         idine    chloro-iso-                                                                   indolinone                                                       53  3-Acetyl-2,4- dihydroxy- quinoline                                                     3-Imino- 4,5,6,7-tetra- chloro-iso- indolinone                                        ##STR26##      orange                                    54  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Amino-5-      orange                                        dihydroxy-                                                                             4,5,6,7-tetra-                                                                       methyl-ben-                                                   quinoline                                                                              chloro-iso-                                                                          zoylamino-                                                             indolinone                                                                           benzimidazole                                             55  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Amino-5-p-    orange                                        dihydroxy-                                                                             4,5,6,7-tetra-                                                                       chloro-ben-                                                   quinoline                                                                              chloro-iso-                                                                          zoylamino-                                                             indolinone                                                                           benzimidazole                                             56  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Amino-5-      scarlet                                       dihydroxy-                                                                             4,5,6,7-tetra-                                                                       benzoylamino-                                                 quinoline                                                                              chloro-iso-                                                                          benzimidazole                                                          indolinone                                                       57  3-Acetyl-2,4-                                                                          3-Imino-5,6-                                                                         2-Amino-benz-   orange                                        dihydroxy-                                                                             dichloro-iso-                                                                        thiazole                                                      quinoline                                                                              indolinone                                                       58  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Aminothia-    orange                                        dihydroxy-                                                                             indolinone                                                                           zole                                                          quinoline                                                                 59  3-Acetyl-2,4-                                                                          3-Imino-5,6-                                                                         2-Amino-5-      red                                           dihydroxy-                                                                             dichloro-iso-                                                                        ethoxy-benz-                                                  quinoline                                                                              indolinone                                                                           imidazolone                                               60  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Amino-benz-   red                                           dihydroxy-                                                                             4,5,6,7-tetra-                                                                       thiazole                                                      quinoline                                                                              chloro-iso-                                                                   indolinone                                                       61  3-Acetyl-2,4-                                                                          3-Imino-                                                                             2-Amino-benz-   red                                           dihydroxy-                                                                             4,5,6,7-tetra-                                                                       imidazole                                                     quinoline                                                                              chloro-iso-                                                                   indolinone                                                       62  3-Acetyl-4-                                                                            3-Imino-                                                                             2-Amino-benz-   orange                                        hydroxy-coum-                                                                          4,5,6,7-tetra-                                                                       imidazole                                                     arin     chloro-iso-                                                                   indolinone                                                       63  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Amino-benz-   orange                                        dihydroxy-                                                                             indolinone                                                                           imidazole                                                     quinoline                                                                 64  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         2-Amino-benz-   orange                                        dihydroxy-                                                                             indolinone                                                                           imidazole                                                     quinoline                                                                 65  3-Acetyl-2,4-                                                                          3-Imino-iso-                                                                         1,4-Diamino-    scarlet                                       dihydroxy-                                                                             indolinone                                                                           phthalazine                                                   quinoline                                                                 66  1-Phenyl-3-                                                                            3-Imino-iso-                                                                         Cyanoacet-      red                                           methyl-4-formyl-                                                                       indolinone                                                                           anilide                                                       5-mercapto-                                                                   pyrazole                                                                  67  1-Phenyl-3-                                                                            3-Imino-iso-                                                                         Cyanoacetic     red                                           methyl-4-formyl-                                                                       indolinone                                                                           acid 4'-phe-                                                  5-mercapto-     noxyanilide                                                   pyrazole                                                                  68  1-Phenyl-3-                                                                            3-Imino-iso-                                                                         Cyanoacetic     red                                           methyl-4-formyl-                                                                       indolinone                                                                           acid 4'-                                                      5-mercapto-     acetylamino-                                                  pyrazole        anilide                                                   69  1-Phenyl-3-                                                                            3-Imino-iso-                                                                         Cyanoacetic     red                                           methyl-4-formyl-                                                                       indolinone                                                                           acid 4'-                                                      5-mercapto-     methyl-                                                       pyrazole        anilide                                                   70  1-Phenyl-3-                                                                            3-Imino-iso-                                                                         Cyanoacetic     red                                           methyl-4-formyl-                                                                       indolinone                                                                           acid 4'-meth-                                                 5-mercapto-     oxyanilide                                                    pyrazole                                                                  71  1-Phenyl-3-                                                                            3-Imino-iso-                                                                         Cyanoacetic     red                                           methyl-4-formyl-                                                                       indolinone                                                                           acid 4'-                                                      5-mercapto-     chloroanilide                                                 pyrazole                                                                  72  1-p-Chlorophenyl-                                                                      3-Imino-4,6-                                                                         Cyanoacet-      Bordeaux                                      3-methyl-4-                                                                            dimethoxy-                                                                           amide           red                                           acetylpyrazol-                                                                         5,7-dichloro-                                                        5-one    isoindolinone                                                    73  1-p-Chlorophenyl-                                                                      3-Imino-5,6-                                                                         Cyanoacet-      red                                           3-methyl-4-                                                                            dichloro-iso-                                                                        amide                                                         acetylpyrazol-                                                                         indolinone                                                           5-one                                                                     74  1-p-Chlorophenyl-                                                                      3-Imino-4,6-                                                                         Cyanoacet-      Bordeaux                                      3-methyl-4-                                                                            dimethoxy-                                                                           amide           red                                           acetylpyrazol-                                                                         5,7-dichloro-                                                        5-one    isoindolinone                                                    75  3-Acetyl-4-                                                                            3-Imino-4,6-                                                                         Cyanoacet-      red                                           hydroxy- dimethoxy-                                                                           amide                                                         coumarin 5,7-dichloro-                                                                 isoindolinone                                                    76  3-Acetyl-4-                                                                            3-Imino-5,6-                                                                         Cyanoacet-      red                                           hydroxy- dichloro-iso-                                                                        amide                                                         coumarin indolinone                                                       77  1-Phenyl-3-al-                                                                         3-Imino-iso-                                                                         Cyanomethyl-    red                                           koxycarbonyl-4-                                                                        indolinone                                                                           benzimida-                                                    formyl-5-mercap-                                                                              zole                                                          topyrazole                                                                78  1-Phenyl-3-thio-                                                                       3-Imino-iso-                                                                         2-Aminobenz-    orange                                        carbamoyl-4-                                                                           indolinone                                                                           imidazole                                                     formyl-5-mer-                                                                 captopyrazole                                                             79  7-Chloro-4-                                                                            3-Imino-iso-                                                                         Cyanoacetic     red                                           methoxy-3-                                                                             indolinone                                                                           acid                                                          formyl-2-mercap-                                                                              p-chloro-                                                     to-quinoline    anilide                                                   __________________________________________________________________________

EXAMPLES 80-82

By reacting the isoindolinone derivative of the formula ##STR27## withthe hydrazone of the formula ##STR28## in the presence of the acetate ofthe metal listed in column 2 of Table 2, analogously to Examples 1-8,further metal complexes of the formula ##STR29## are obtained (forreasons of simplicity, only one of the possible isomeric or tautomericforms is considered), M being the metal indicated in column 2. Column 3gives against the shade of the colouration in polyvinyl chloride.

                  TABLE 2                                                         ______________________________________                                        Example No.     M     Shade in PVC                                            ______________________________________                                        80              Pd    red                                                     81              Cu    red                                                     82              Zn    scarlet-red                                             ______________________________________                                    

EXAMPLE 83

25 parts of the pigment prepared according to Example 1, 100 parts offinely ground sodium chloride and 30 parts of diacetone-alcohol areinitially introduced into a laboratory kneader with a capacity of 250parts by volume. The mixture is kneaded for 5 hours, with cooling, andthen introduced into 4,000 parts by volume of water. The sodium chlorideand diacetone-alcohol dissolve and the pigment precipitates out. Thesuspension is filtered and the material on the suction filter is washedthoroughly with water and dried in a vacuum drying cabinet at 80°.

EXAMPLE 84

65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalateand 0.2 part of the pigment obtained according to Example 76 are stirredwith one another and then worked on a twin-roll mill for 7 minutes at140°. A red-coloured sheet with very good fastness to light andmigration is obtained.

EXAMPLE 85

10 g of titanium dioxide and 2 g of the pigment prepared according toExample 76 are ground with 88 g of a mixture of 26.4 g of coconut alkydresin, 24.0 g of melamine/formaldehyde resin (50% solids content), 8.8 gof ethylene glycol monomethyl ether and 28.8 g of xylene, for 48 hoursin a ball mill.

If this surface coating is sprayed onto an aluminium foil, predried for30 minutes at room temperature and then stoved for 30 minutes at 120°C., a red coating is obtained, which had good colour intensity and isdistinguished by a very good fastness to overcoating, light and weather.

EXAMPLE 86

4 parts of the finely divided pigment according to Example 76 stirredinto 20 parts of solvent of the following composition: 50 parts ofSolvesso 150 (mixture of aromatic hydrocarbons), 15 parts of butylacetate, 5 parts of Exkin II (ketoxime-based levelling agent), 25 partsof methyl isobutyl ketone and 5 parts of silicone oil (1% in Solvesso150).

After complete fine dispersion has been reached (in about 15-60 minutes,depending on the type of stirrer), the binders are added, i.e. 48.3parts of Baycryl L 530 (acrylic resin) (51% in xylene/butanol 3:1) and23.7 parts of Maprenal TTX (melamine resin) (55% in butanol).

After a short period of homogenisation, the surface coating is appliedby customary methods, such as spraying and dipping or, especially forthe continuous coating of metal sheets, by the "coil-coating" process,and stoved (stoving: 30 minutes, 130°). The red coatings obtained aredistinguished by very good levelling, high gloss and excellent finedispersion of the pigment, and also by excellent fastness to weather.

EXAMPLE 87

If the procedure described in Example 83 is repeated, except that 2.78parts of Staybelite Resin (HERCULES) are added to the kneading mixture,a pigment containing 10% of resin is obtained, which is distinguished bybeing easier to incorporate and by better dispersibility.

What is claimed is:
 1. A process for the preparation of a 1:1 metalcomplex of an azine of the formula ##STR30## in which R₁ is hydrogen,alkyl or aryl, ring A is unsubstituted or is substituted by groups whichdo not confer solubility in water, Y' is a radical of the formula##STR31## in which R' is a cyano group, an alkoxycarbonyl,alkylcarbamoyl or alkanoyl group having 2-6 C, a benzoyl, carbamoyl orsulfamoyl group, a benzylcarbamoyl or a phenylsulfamoyl orphenylsulfonyl group which is unsubstituted or substituted by halogenatoms or alkyl groups having 1-4 C, a group of the formula ##STR32## inwhich X₁ is an H, chlorine or bromine atom, a nitro, trifluoromethyl,carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl grouphaving 1-4 C, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl grouphaving 2-6 C, or a phenoxy, benzoylamino, phenylcarbamoyl,phenylsulfamoyl or phenylazo group which is unsubstituted or substitutedby chlorine or bromine atoms or methyl groups, X₂ is an H, chlorine orbromine atom or an alkyl or alkoxy group having 1-4 C and V is O, S orNH,Q is ##STR33## where B is a phenyl or naphthalene radical or a 5- or6-membered heterocyclic ring which has an O, S or N atom in the α- orγ-position to the C atom on which the hydroxyl or mercapto group islocated, and may also contain a further N atom in the ring or contain afused benzene ring and/or a further heterocyclic ring, which processcomprises heating a hydrazone of the formula ##STR34## with anisoindolinone of the formula ##STR35## in which R₁, Q, A and Y' are asdefined above, in the presence of a metal donor, in a polar organicsolvent.
 2. A process according to claim 1 where in the hydrazone R₁ ishydrogen or methyl, and Q is a radical containing a pyrazole, pyridine,pyrimidine, quinoline or coumarin moiety.
 3. A process according toclaim 1 where in the hydrazone R₁ is a hydrogen or methyl, and Q is aradical of the formula ##STR36## in which X₃ and X₄ independently of oneanother are H, Hal or alkyl having 1-4 C.
 4. A process according toclaim 1 where in the isoindolinone of formula (3) ring A isunsubstituted.
 5. A process according to claim 1, which comprisesstarting from an isoindolinone of the formula (3) in which Y' is theradical of the formula ##STR37## in which V, X₁ and X₂ are as defined inclaim
 1. 6. A process according to claim 1, which comprises using anickel salt as the metal donor.
 7. A process according to claim 1, whichcomprises using dimethylformamide or N-methylpyrrolidone as the polarsolvent.
 8. A process according to claim 1, which comprises carrying outthe reaction at temperatures between 100° and 200°.